Properties

Nitrogen is a nonmetal, with an electronegativity of 3.0. It has five electrons in its outer shell and is therefore trivalent in most compounds. The triple bond in molecular nitrogen (N2) is one of the strongest in nature. The resulting difficulty of converting (N2) into other compounds, and the ease (and associated high energy release) of converting nitrogen compounds into elemental N2, have dominated the role of nitrogen in both nature and human economic activities.

Unstable allotropes of nitrogen consisting of more than two nitrogen atoms have been produced in the laboratory, like N3 and N4.[1] Under extremely high pressures (1.1 million atm) and high temperatures (2000 K), as produced under diamond anvil conditions, nitrogen polymerizes into the single bonded diamond crystal structure, an allotrope nicknamed "nitrogen diamond."[2]

Occurrence

Nitrogen is the largest single constituent of the Earth's atmosphere (78.082% by volume of dry air, 75.3% by weight in dry air). It is created by fusion processes in stars, and is estimated to be the 7th most abundant chemical element by mass in the universe.

Nitrogen is present in all living organisms in proteins, nucleic acids and other molecules. It is a large component of animal waste (for example, guano), usually in the form of urea, uric acid, ammonium compounds and derivatives of these nitrogenous products, which are essential nutrients for all plants that are unable to fix atmospheric nitrogen.

Isotopes

There are two stable isotopes of nitrogen: 14N and 15N. By far the most common is 14N (99.634%), which is produced in the CNO cycle in stars and the remaining is 15N. Of the ten isotopes produced synthetically, 13N has a half life of ten minutes and the remaining isotopes have half lives on the order of seconds or less.
Biologically-mediated reactions (e.g., assimilation, nitrification, and denitrification) strongly control nitrogen dynamics in the soil. These reactions typically result in 15N enrichment of the substrate and depletion of the product.

0.73% of the molecular nitrogen in Earth's atmosphere is comprised of the isotopologue14N15N and almost all the rest is 14N2.

Electromagnetic spectrum

Molecular nitrogen (14N2) is largely transparent to infrared and visible radiation because it is a homonuclear molecule and thus has no dipole moment to couple to electromagnetic radiation at these wavelengths. Significant absorption occurs at extreme ultraviolet wavelengths, beginning around 100 nanometers. This is associated with electronic transitions in the molecule to states in which charge is not distributed evenly between nitrogen atoms. Nitrogen absorption leads to significant absorption of ultraviolet radiation in the Earth's upper atmosphere as well as in the atmospheres of other planetary bodies. For similar reasons, pure molecular nitrogen lasers typically emit light in the ultraviolet range.

Nitrogen also makes a contribution to visible air glow from the Earth's upper atmosphere, through electron impact excitation followed by emission. This visible blue air glow (seen in the polar aurora and in the re-entry glow of returning spacecraft) typically results not from molecular nitrogen, but rather from free nitrogen atoms combining with oxygen to form nitric oxide (NO).

Applications

Liquid nitrogen

Liquid nitrogen is a cryogenic liquid. At atmospheric pressure, it boils at −196.5 °C. When insulated in proper containers such as dewar flasks, it can be transported without much evaporative losses.

Like dry ice, the main use of liquid nitrogen is as a refrigerant. Among other things, it is used in the cryopreservation of blood, reproductive cells (sperm and egg), and other biological samples and materials. It is also used in cold traps for certain laboratory equipment. It has also been used to cool central processing units and other devices in computers which are overclocked, and which produce more heat than during normal operation.

Biological role

Specific bacteria (e.g. Rhizobium trifolium) possess nitrogenaseenzymes which can fix atmospheric nitrogen (see nitrogen fixation) into a form (ammonium ion) which is chemically useful to higher organisms. This process requires a large amount of energy and anoxic conditions. Such bacteria may be free in the soil (e.g. Azotobacter) but normally exist in a symbiotic relationship in the root nodules of leguminous plants (e.g. clover, Trifolium species, or the soy bean plant, Glycine max). Nitrogen-fixing bacteria can be symbiotic with a number of unrelated plant species. Common examples are legumes, alders (Alnus) spp., lichens, Casuarina, Myrica, liverworts, and Gunnera.

As part of the symbiotic relationship, the plant subsequently converts the ammonium ion to nitrogen oxides and amino acids to form proteins and other biologically useful molecules, such as alkaloids. In return for the usable (fixed) nitrogen, the plant secretes sugars to the symbiotic bacteria.

Nitrogen compounds are basic building blocks in animal biology. Animals use nitrogen-containing amino acids from plant sources, as starting materials for all nitrogen-compound animal biochemistry, including the manufacture of proteins and nucleic acids. Some plant-feeding insects are so dependent on nitrogen in their diet, that varying the amount of nitrogen fertilizer applied to a plant can affect the rate of reproduction of the insects feeding on it.[3]

Nitrogen compounds in industry

Simple compounds

The main neutral hydride of nitrogen is ammonia (NH3), although hydrazine (N2H4) is also commonly used. Ammonia is more basic than water by 6 orders of magnitude. In solution ammonia forms the ammoniumion (NH4+). Liquid ammonia (b.p. 240 K) is amphiprotic (displaying either Brønsted-Lowry acidic or basic character) and forms ammonium and the less common amide ions (NH2-); both amides and nitride (N3-) salts are known, but decompose in water. Singly, doubly, triply and quadruply substituted alkyl compounds of ammonia are called amines (four substitutions, to form commercially and biologically important quarternary amines, results in a positively charged nitrogen, and thus a water-soluble, or at least amphiphilic, compound). Larger chains, rings and structures of nitrogen hydrides are also known, but are generally unstable. N22+ is another polyatomic cation as in hydrazine.

Other classes of nitrogen anions (negatively charged ions) are the poisonous azides (N3-), which are linear and isoelectronic to carbon dioxide, but which bind to important iron-containing enzymes in the body in a manner more resembling cyanide. Another molecule of the same structure is the colorless and relatively inert anesthetic gas dinitrogen monoxide (N2O), also known as laughing gas. This is one of a variety of oxides, the most prominent of which are nitrogen monoxide (NO) (known more commonly as nitric oxide in biology), a natural free radical molecule used by the body as a signal for short-term control of smooth muscle in the circulation. Another notable nitrogen oxide compound (a family often abbreviated NOx) is the reddish and poisonous nitrogen dioxide (NO2), which also contains an unpaired electron and is an important component of smog. Nitrogen molecules containing unpaired electrons show an understandable tendency to dimerize (thus pairing the electrons), and are generally highly reactive.

Nitrogen compounds of notable economic importance

Nitrogen is a constituent of molecules in every major drug class in pharmacology and medicine. Nitrous oxide (N2O) was discovered early in the 19th century to be a partial anesthetic, though it was not used as a surgical anesthetic until later. Called "laughing gas", it was found capable of inducing a state of social disinhibition resembling drunkenness. Other notable nitrogen-containing drugs are drugs derived from plant alkaloids, such as morphine (there exist many alkaloids known to have pharmacological effects; in some cases they appear natural chemical defences of plants against predation). Nitrogen containing drugs include all of the major classes of antibiotics, and organic nitrate drugs like nitroglycerin and nitroprusside which regulate blood pressure and heart action by mimicking the action of nitric oxide.

Dangers

Rapid release of nitrogen gas into an enclosed space can displace oxygen, and therefore represents an asphyxiation hazard. This may happen with few warning symptoms, since the human carotid body is a relatively slow and a poor low-oxygen (hypoxia) sensing system.[4] An example occurred shortly before the launch of the first Space Shuttle mission in 1981, when two technicians lost consciousness and died after they walked into a space located in the Shuttle's Mobile Launcher Platform that was pressurized with pure nitrogen as a precaution against fire. The technicians would have been able to exit the room if they had experienced early symptoms from nitrogen-breathing.

When inhaled at high partial pressures (more than about 3 atmospheres, encountered at depths below about 30 m in scuba diving) nitrogen begins to act as an anesthetic agent. It can cause nitrogen narcosis, a temporary semi-anesthetized state of mental impairment similar to that caused by nitrous oxide.

Nitrogen also dissolves in the bloodstream and body fats, and rapid decompression (particularly in the case of divers ascending too quickly, or astronauts decompressing too quickly from cabin pressure to spacesuit pressure) can lead to a potentially fatal condition called decompression sickness (formerly known as caisson sickness or more commonly, the "bends"), when nitrogen bubbles form in the bloodstream, nerves, joints, and other sensitive or vital areas.

Direct skin contact with liquid nitrogen causes severe frostbite (cryogenic burns) within seconds, though not instantly on contact, depending on form of liquid nitrogen (liquid vs. mist) and surface area of the nitrogen-soaked material (soaked clothing or cotton causing more rapid damage than a spill of direct liquid to skin, which for a few seconds is protected by the Leidenfrost effect).